Method and composition for fulling fabrics



United States. Patent M 3,104,443 METHOD AND COMPGSITEON FQR FULLENGFABRIQS Frederick T. Lense, Birmingham, Ala, assiguor to MonsantoChemical Company, St. Louis, Me, a corporation of Delaware N0 Drawing.Filed Dec. 4, 1957, filer. No. 700,543 Claims. (QB. 26-49) Thisinvention relates to fulling and/or felting of fabrics containing W001and other animal fibers such as carnels hair, rabbit hair, etc. Oneparticularly preferred embodiment of this invention relates to methodsand compositions for fulling and/ or felting wool fabrics, andespecially for fulling and/or felting such fabrics in the presence of anacid bath.

In the past, the foregoing treatments of animal fiber fabrics (-i.e.,fabrics made up either completely or only partly of such animal fibers)have been largely carried out in aqueous solutions containing soaps.These soaps served several purposes, among which were lubrication andcleansing of the fabric. Since soaps are completely ineffective in acidmedia and relatively ineffective in neutral media, it has been necessaryto maintain the solutions containing such soaps in an alkaline pHrangein spite of the fact that alkaline solutions tend to attack anddegrade wool.

With the relatively recent advent and commercial availability ofnon-ionic surface-active agents (which retain their surface activityeven in acidic solutions), therehas been a tendency for fabricprocessers to change their processing operations from alkaline fullingand/or felting to acidic fulling and/or felting with non-ionicsurface-active agents. This has been effected by using common acids suchas sulphuric acid, acetic acid, orthophosphoric acid, etc. to acidifythe aqueous solutions of nonionic surface-active agents.

It has now been found that unexpectedly outstanding beneficial resultsare obtained by utilizing a fulling and/or felting solution containing(in addition to a non-ionic surface-active agent) an alkylarenesulfonicacid. More particularly it has been found that a combination of certainalkylarenesulfonic acids and non-ionic surface-active agents will givesynergistic results in acid fulling and/or felting of woolfabrics-particularly with respect to removal of dirt and oil from thefabric.

The particular alkyl'arenesulfonic acids which must be utilized in thepresent invention are those containing an aromatic nucleus, at least onesulfonic acid group (-SO H), and at least one long-chain alkyl group(e.g., an alkyl group containing between about 6 to about 25 carbonatoms, and preferably between about 9 and about carbon atoms). Thepreferred aromatic nucleus is a benzene ring, but naphthalene, biphenyl,indole, or higher aromatic carbocyclic ring systems, or other cycliccompounds containing an aromatic type resonance (e.g., heterocycliccompounds such as pyridine, quinoline, thiophene, and the like) can alsobe utilized.

The alkylarenesulfonic acids can contain more than one of the long-chainialkyl groups, and can also contain (in addition to the one or morelong-chain alkyl groups) one or more shorter alkyl groups such asmethyl, ethyl, propyl, etc. radicals. In general, particularly from thepoint of view of simplicity, availability, and water BJMAQ PatentedSept. 24, 1963 solubility, the monoalkyl substituted sulfonic acids (orat least the sulfonic acids containing only one of the longchain alkylgroups) are preferred over the more highly substituted sulfonic acids.Likewise, the present sulfonic acids can contain more than one sulfonicacid group (e.g., as in diand trisulfonic acids), but in general themonosulfonic acids are preferred. From the foregoing it will be apparentthat a particularly preferred embodiment of this invention involves theuse of monoalkylbenzenesulfonic acids in the acid fulling and/or feltingof woolen and other animal fiber fabrics.

Typical examples of the above-discussed alkylarenesulfonic acids are:n-hexylbenzenesulfonic acid; Z-ethylhexylbenzenesulfonic acid;nonyltoluenesulfonic acids (especially those in which the nonyl group isderived from a propylene trimer); n-decylxylenesulfonic acid;n-decylnaphthalenedisulfonic acid; 3-n-dodecyl-5-ethylbenzenesulfonicacid; dodecyl and tridecylbenzenesulfonic acids (wherein the dodecylandtridecylbenzenes are obtained by alkylation of benzene with propylenetetra mer or butylene trimer); n-tetradecyltoluenedisulionic acid;n-hexadecylbenzenesulfonic acid; octadecylbenzenedisulfonic acid; andthe like. Although the foregoing compounds have been referred to asspecific materials, it will be readily appreciated that they willgenerally occur and be used as the isomeric mixtures which normallyresult from alkylation of the particular aromatic nucleus in questionand subsequent sulfonation of the alkylated aromatic compound.

The other essential component of the aqueous acidic baths of the presentinvention is a non-ionic surface-active agent-numerous examples of whichare well known and commercially available. Particularly preferredcategories of such non-ionic synthetic surface-active agents are (1)condensation products of ialkylphenols and ethylene oxide, (2)condensation products of aliphatic alcohols and ethylene oxide, (3)condensationproducts of aliphatic mercaptans and ethylene oxide, and (4)condensation products containing both ethylene oxide and propyleneoxide. Further elaboration with respect to these preferred categories isset forth below:

(1) CONDENSATION PRODUCTS OF ALKYL- PHENOLS AND ETHYLENE OXIDE The alkylgroups on the alkylphenols should generally contain between about 6 andabout 20 carbon atoms, and preferably between about 8 and about 15carbon atoms. While :alkylphenols containing more than one alkyl groupper phenol nucleus can be utilized, it is generally preferred to usemonoalkylphenols. The amount of ethylene oxide to be condensed with thealkylphenols depend to some extent upon the size and number of saidalkyl groups. In general, between about 4 and about '15 mols, andpreferably between about 6 and about 12 mols, ofethylene oxide will becondensed with each mol of alkylpheno-lthe higher proportions ofethylene oxide being utilized with the phenols containing the largernumber of carbon atoms in the alkyl groups. Typical examples of theforegoing category of alkylphenol/ ethylene oxide nonionic syntheticdetergents are condensation products of 1 mol of n-hexylphenol and 5mols of ethylene oxide; 1 mol of Z-ethylhexylphenol and 6 rno-ls ofethylene oxide; 1 mol of n-octylphenol and '6 mols of ethylene oxide; 1mol of nonylphenol (obtained by alkylation of phenol with a trimer ofpropylene) and 10 mols of ethylene oxide; 1 mol of n-decylphenol and 8mols of ethylene oxide; 1 mol of n-dodecylphenol and 14 mols of ethyleneoxide; 1 mol of dodecylphenol (from alkylation of a phenol withpropylene tetrarner or butylene trimer) and 12 mols of ethylene oxide; 1mol of n-octadecylphenol and 15 rnols of ethylene oxide.

(2) CONDENSATION PRODUCTS OF ALIPHATIC ALCOHOLS AND ETHYLENE OXiDE Thealiphatic alcohols utilized in these condensates are long-chained alkylalcohols containing between about 10 and about 20 carbon atoms, andpreferably between about 12 and about 16 carbon atoms. As in the case ofthe alkylphenol condensation products, the amount of ethylene oxide tobe condensed with such alcohols will depend to some extent upon thenumber of carbon atoms in the alcohol. In general, between about 4 andabout 15 mols of ethylene oxide, and preferably between about 5 andabout 12 mols of ethylene oxide will be condensed with each mol ofalcohol. Typical condensates of this category are as follows: 1 mol ofdecyl alcohol and 4 mols of ethylene oxide; 1 mol of n-dodecyl alcoholand 5 mols of ethylene oxide; 1 mol of tridecyl alcohol (e.g., the oxoalcohol prepared from propylene stetramer or butylene trimer) and 5 molsof ethylene oxide; 1 mol of oxo-tridecyl alcohol and 9 mols of ethyleneoxide; 1 mol of 0x0- tridecyl alcohol and 15 mols of ethylene oxide; 1mol of n-tetradecyl alcohol and 8 mols of ethylene oxide; 1 mol ofn-hexadecyl alcohol and 12 mols of ethylene oxide; 1 mol of n-octadecylalcohol and mols of ethylene oxide; 1 mol of eicosyl alcohol and 14 molsof ethylene oxide.

(3) CONDENSATION PRODUCTS OF ALIPHATIC MERCAPTANS AND ETHYLENE OXIDE Thealiphatic mercaptans utilized in these condensates are long-chain alkylmercaptans containing between about 8 and about 20 carbon atoms, andpereferably between about 9 and about carbon atoms. As in theabovediscussed categories, the amount of ethylene oxide to be condensedwith such mercaptans Will depend upon the chain length of the alkylportion of the mercaptan, but will generally range from about 4 to about15 mols, and preferably from about 7 to about 12 mols of ethylene oxideper mol of mercaptan. Typical examples of such condensation products areas follows: 1 mol of 2-ethylhexyl mercaptan and 4 mols of ethyleneoxide; 1 mol of n-octyl mercaptan and 6 mols of ethylene oxide; 1 mol ofn-decyl mercaptan and 7.5 mols of ethylene oxide; 1 mol of nonylmercaptan (e.g., from propylene trimer) and 8 mols of ethylene oxide; 1mol of branched-chain dodecyl mercaptan (e.g., from propylene tetrameror butylene trimer) and 10 mols of ethylene oxide; 1 mol of n-tetradecylmercaptan and 11 mols of ethylene oxide; 1 mol of n-octadecyl mercaptanand 10 mols of ethylene oxide; 1 mol of eicosyl mercaptan and 14 mols ofethylene oxide.

(4) CONDENSATION PRODUCTS OF BOTH ETHYLENE OXIDE AND HIGHER ALKYLENEOXIDES These products are of the type often referred to as blockpolymers of ethylene oxide and higher alkylene oxides, of whichcondensation products of ethylene oxide and propylene oxide (with orwithout fatty acids, alcohols, mercaptans, alkylphenols, etc.) arepreferred materials. Typical examples of these latter categories arethose described in U.S. 2,674,619 and US. 2,677,700, the disclosures ofwhich are incorporated herein by reference.

It should be understood that the categories of non-ionic syntheticsurface-active agents discussed .above are merely preferred categories,and that the present invention is not limited to the use of only thosenon-ionic surface-active agents. For example, the well known class ofnon-ionic surface-active agents made up of condensation products aroaaasof long-chain aliphatic acids and ethylene oxide can also be utilized,as well as many others with which those skilled in the art will befamiliar.

The foregoing sulfonic acids and non-ionic surfaceactive agents areformulated and used in amounts to give a weight ratio of sulfonic acidto non-ionic surface-active agents between about 1:5 and about 5:1, andpreferably between about 1:3 and about 1:1. For convenience in handlingand shipping, the combination of sulfonic acid and ncnionicsurfacecctive agents 'will often be formulated in concentrated form,said concentrates to be solved and diluted with considerable proportionof water for utilization in treating fabrics according to the presentinvention. in actual use, between about 0.2 and about 20 ounces,preferably between about 2 and about 5 ounces, of the mixture ofsulfonic acid and non-ionic surface-active agents will be dissolved ineach gallon of water utilized in the aqueous treating solution.

In preparing concentrates of the sulfonic acids and nonionicsurface-active agents it will generally be desirable to incorporatebetween about 5 and about 20% by weight (based upon the totalconcentrate) of water in order to reduce the viscosity of theconcentrate and make it easier to handle and dilute for ultimate use.

The solutions utilizing the combination of materials described hereinmust be maintained in .an acidic pH range (i.e., pH less than 7). Theyare preferably maintained at a pH between about 2 and about 5. Ifnecessary or desirable, other acids (such as sulfuric acid, acetic acid,phosphoric acid, etc.) may be used (in addition to the aforedescribedingredients) in order to maintain the pH in the desired range. Theseother acids can also be used to produce the compositions of the presentinvention from mixtures of a non-ionic surface-active agent and analkylarenesulfonate salt. Thus, for example, a mixture of sodiumdodecylbenzene sulfonate and a non-ionic surface-active agent can beacidified with sulfuric acid to produce a mixture of the sulfonic acid,the non-ionic agent and sodium sulfate. When used as described herein(particularly in solutions having pH less than about 5) the sodiumsulfate will merely behave as an inert diluent not having any particulareffect upon the utility of the essential components, i.e., the sulfonicacid and the non-ionic surface-active agent.

The operations using the ingredients described in this invention can becarried out in the same manner as any of the prior art fulling and/orfelting operations-particularly acid fulling and/or felting operations.Since such operations and practices are well known to those skilled inthe textile art, the details thereof will not be repeated here.

The following example will serve to illustrate the outstanding andbeneficial results obtained when using solutions formulated according tothe present invention:

Example Loomstate wool fiber fabrics were processed in a laboratoryfulling mill in the presence of solutions containing the variousingredients indicated in the following table. The fabric was fulled for15 minutes, rinsed with water, and then analyzed with respect to (1) theamount of oil remaining in the fabric and (2) the effectiveness withwhich dirt had been removed from the fabric. The results are set forthin the accompanying table. From the table it is apparent that thecombination of sulfonic acids and non-ionic detergents of this inventionare much more effective than either of the components taken aloneevenwhen the individual component alone is used at a concentration as greatas that of the combination. The results also demonstrate that the elfectof the sulfonic acid is not merely one of acidifying the solution, sinceacidification with the more common acids (e.g., sulfuric acid) does notproduce a comparable result. It was also noted that the acid solutionsof the present invention were particularly 5 outstanding with respect tothe ease with which .they are rinsed from the processed fabric with onlya water rinse.

thereof and (b) between 0.2 and 5 parts by weight of a condensationproduct of an alkylphenol containing from TABLE Additives Oil ContentAfter Test Dirt Fulling N on-Ionic Surface-Active Removal andAlkylarenesulfonie Acid Agent (Condensation Rinsing, Products) Percent AWater Only Very Poor.-. 3. 91 B. Dodecylbenzenesulfonic Poor- 2.91

Acid (3 oz./gal. H20). tert.-Do(lecylmercaptan+ Good 2. 37

7.8 E.O (3oz./gal.H2O). D tert.-D0clecylmercaptau+ do 1. 28

7.8 12.0 (3 ozJgal. H2O, plus H1504 to bring pH of bath to 3.0). EDodecylbenzenesulfonic tert.-Dodecyhnercaptau+ Excellent. 0. 41

Acid (1 oz./gal. H10). 7.8 E.(). (2oz./gal. H20). FDodecylbenzenesultonic Oxo-tridecyl alcohol+9 do 0. 13

Acid (1.5 oz./gal. E.O. (1.5 0z./gal. H 0). 20).

I claim: about 8 to about 15 carbon atoms 1n the alkyl group 1. Acomposition of matter comprising (a) one part by weight of analkylbenzenesulfonic acid containing from about 6 to about 25 carbonatoms in the alkyl group thereof and (b between about 0.2 and aboutparts by weight, for each part by weight of said acid, of a nonionicsynthetic surface-active agent selected from the group consisting of (1)a condensation product of an alkylphenol containing from about 6 toabout 20 carbon atoms in the alkyl group thereof with between about 4and about 15 molar proportions of ethylene oxide, (2) a condensationproduct of an aliphatic alcohol containing from about to about 20 carbonatoms therein with between about 4 and about molar proportions ofethylene oxide and (3) a condensation product of an aliphatic mercaptancontaining from about 8 to about carbon atoms therein with between about5 and about 15 molar proportions of ethylene oxide.

2. A composition of matter comprising (a) 1 part by weight of analkylbenzenesulfonic acid containing from about 6 to about carbon atomsin the alkyl group thereof and (b) between about 3 and about 1 part byweight of a non-ionic synthetic surface-active agent selected from thegroup consisting of (1) a condensation product of an alkylphenolcontaining from about 6 to about 20 carbon atoms in the alkyl groupthereof with between about 4 and about 15 molar proportions of ethyleneoxide, (2) a condensation product of an aliphatic alcohol containingfrom about 10 to about 20 carbon atoms therein with between about 4 andabout 15 molar proportions of ethylene oxide and (3) a condensationproduct ofan aliphatic mercaptan containing from about 8 to about 20carbon atoms therein with between about 5 and about 15 molar proportionsof ethylene oxide.

3. A composition of matter comprising (a) one part by weight of analkylbenzenesulfonic acid containing from about 9 to about 15 carbonatoms in the alkyl group thereof and (b) between about 0.2 and about 5'parts by weight of a condensation product of an aliphatic mercaptancontaining from about 9' to about 15 carbon atoms therein with betweenabout 7 and about 12 molar proportions of ethylene oxide.

4. A composition of matter comprising (a) one part by weight of analkylbenzenesulfonic acid containing from about 9 to about 15 carbonatoms in the alkyl group thereof and (b) between about 0.2 and about 5parts by weight of a condensation product of an aliphatic alcoholcontaining from about 12 to about 16 carbon atoms therein with betweenabout 5 and about 12 molar proportions of ethylene oxide.

5. A composition of matter comprising (a) one part by weight of analkylbenzenesulfonic acid containing from about 9 to about 15 carbonatoms in the alkyl group thereof with between about 6 and about 12 molarproportions of ethylene oxide.

6. A composition of matter comprising (a) one part by weight of analkylbenzenesulfonic acid containing from about 6 to about 25 carbonatoms in the alkyl group thereof; (b) between about 0.2 and about 5parts by weight of a non-ionic synthetic detergent selected from thegroup consisting of (1) a condensation product of an alkylphenolcontaining from about 6 to about 20 carbon atoms in the alkylgroupthereof with between about 4 and about 15 molar proportions of ethyleneoxide, (2) a condensation product of an aliphatic alcohol containingfrom about 10 to about 20 carbon atoms therein with between about 4 andabout 15 molar proportions of ethylene oxide and (3) a condensationproduct of an aliphatic mercaptan containing from about 8 to about 20carbon atoms therein with between 5 and about 15 molar proportions ofethylene oxide; and (c) between about 5% and about 20% by weight ofwater (based upon the total weight of the mixture).

7. A composition of matter comprising (a) about 30% by weight ofdodecylbenzenesulfonic acid; (b) about 60% by weight of the condensationproduct of tertiary dodecylmercaptan with about 8 molar proportions ofethylene oxide; and (0) about 10% by weight of water.

8. In a process of fulling fabrics, the improvement which comprisesperforming the said fulling with said fabrics being wetted with anaqueous solution of a mixture of (a) an alkylbenzenesulfonic acidcontaining from about 6 to about 25 carbon atoms in the alkyl groupthereof and (b) a non-ionic synthetic surface-active agent; said fullingbath being maintained at a pH between about 2 and about 7, and theweight ratio of said alkylbenzenesulfonic acid to said non-ionic surfaceactive agent in said aqueous solution being between about 1:5 and about5:1.

9. In a process of fulling wool fabrics, the improvement which comprisesperforming the said fulling with said wool fabrics being wetted with anaqueous solution containing between about 2 and about 5 ounces (pergallon of water) a mixture of (a) about one part by weight ofdodecylbenzenesulfonic acid and (b) about two parts by weight of acondensation product of tertiary dodecyl mercaptan with about 8 molarproportions of ethylene oxide; said solution being maintained at a pHbetween about 2 and about 5.

10. A process for the fulling of woolen fabric which comprises applyingto said fabric an aqueous solution having a pH between about 2 and about7 and containing between about 2 and about 5 ounces (per gallon of saidaqueous solution) of a mixture of an alkylbenzenesulfonic acid and anon-ionic synthetic surface active agent, and subjecting said fabriccontaining said aqueous solution to mechanical working in a fullingmachine, the Weight ratio of said alkylbenzenesulfonic acid to saidnon-ionic surface active agent in said mixture being between about 1:5and about 5:1.

References Cited in the file of this patent UNITED STATES PATENTSDaimler et a1 June 4, 1929 Schoeller et a1 Aug. 21, 1934 OTHERREFERENCES Textile World, August 1932, p. 80 (256).

8. IN A PROCESS OF FULLING FABRICS, THE IMPROVEMENT WHICH COMPRISESPERFORMING THE SAID FULLING WITH SAID FABRICS BEING WETTED WITH ANAQUEOUS SOLUTION OF A MIXTURE OF (A) AN ALKYLBENZENESULFONIC ACIDCONTAINING FROM ABOUT 6 TO ABOUT 25 CARBON ATOMS IN THE ALKYL GROUPTHEREOF AND (B) A NON-IONIC SYNTHETIC SURFACE-ACTIVE AGENT; SAID FULLINGBATH BEING MAINTAINED AT A PH BETWEEN ABOUT 2 AND ABOUT 7, AND THEWEIGHT RATIO OF SAID ALKYBENZENESULFONIC ACID, TO SAID NON-IONIC SURFACEACTIVE AGENT IN SAID AQUEOUS SOLUTION BEING BETWEEN ABOUT 1:5 AND ABOUT5:1.